Expanded polymer pellets

Abstract

To provide an expanded polymer pellet that can be manufactured in a process range as wide as possible and can be further processed for forming stable parts usable in wide range applications: for example, manufacturing parts having attenuation characteristics and low weight.SOLUTION: The invention relates to a method for manufacturing an expanded polymer pellet, including a step for melting a polymer containing polyamide; a step for adding at least one foaming agent; a step for expanding a molten article through at least one die for manufacturing an expanded polymer; a step for pelleting the expanded polymer.SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] The present invention relates to a method for producing expanded polymer pellets, whereby The resulting polymer pellets can also be used for, for example, sports apparel or athletic shoes. The present invention further relates to their use, for example for producing cushioning elements. Method for the production of molded components using stretched polymer pellets, and the use of these articles, for example for soundproofing. [Background technology]

[0002] Expanded polymers or polymer foams are well known in the prior art. From publication no. 2006 / 077395, closed-cell polyamide foams are known. These are manufactured in sheets and further processed, for example to form seals. It can be done.

[0003] WO 2006 / 045513 and EP 1650 The 255 patent discloses a crosslinking copolymer having polyamide blocks and polyether blocks. The manufacture of the bridge foam and uses of the foam are described. The brochure concerns expandable, blowing agent-containing thermoplastic polyurethanes of a particular hardness. Similarly, WO 2010 / 010010 discloses a thermoplastic polyurethane. Expandable, blowing agent-containing thermoplastic polymer blends comprising styrene and styrene polymers DE 2011 / 108744 A1 describes a method for the production of shoe soles. The method targets polyurethane (TPU)-based or polyether-based Made from a foamed thermoplastic elastomer based on polybutadiene amide (PEBA) A plastic body is used. Summary of the Invention [Problem to be solved by the invention]

[0004] In contrast, the object of the present invention is to produce a material having as wide a processing window as possible. In order to create stable parts that can be used in a wide range of applications, Expanded polymer particles that can be further processed to produce parts with high flexibility and low weight. A further object is to provide a molded article from the expanded polymer pellets. The object of the present invention is to provide an improved method for the manufacture of a molded component or article. [Means for solving the problem]

[0005] According to a first aspect, the object is to a. melting a polymer comprising a polyamide; b. adding at least one blowing agent; c. expanding the melt through at least one die to produce an expanded polymer causing; and d. pelletizing the expanded polymer; The problem is solved by a method for producing expanded polymer pellets, comprising:

[0006] The present invention further relates to the polymer pellets produced by this method, as well as, for example, For the manufacture of cushioning elements for sports apparel, in particular the soles or soles of athletic shoes The invention further relates to a method for manufacturing such a shoe sole. The present invention relates to shoes, particularly sports shoes, having such a structure.

[0007] The polyamides are, for example, polyamides, copolyamides and / or polyamides as a base. In addition, the polyether block amide may have the following characteristics: : - Shore D hardness ranging from 20 to 70 Shore D; - tensile modulus in the range of 10 to 1100 MPa; - 1 to 9, in each case based on 100% by weight of polyether block amide 0% by weight, preferably 1 to 75% by weight, more preferably 1 to 50% by weight of a polyether 10 to 99% by weight, preferably 25 to 99% by weight, more preferably Preferably, a polyamide block content of 50 to 99% by weight; - 1000 to 1030 g / m 3 Density in the range of; and - Melting point / melting range of 110 to 200°C; may comprise at least one of:

[0008] The blowing agent may be nitrogen, carbon dioxide, ethanol, isopropanol, or a mixture thereof. In addition, a nucleating agent, a chain extender, or both may be added in step b. It is possible.

[0009] The die can be a circular die. The pressure at the die is between 70 and 250 bar. The mass temperature at the die can range from 150°C to 170°C. It could be in the vicinity.

[0010] The swollen polymer may be pelletized in an underwater pelletizer.

[0011] A further aspect of the present invention is the expanded polyamide obtainable by the method described above. Regarding polymer pellets. The pellets have a diameter of 2 to 10 mm, measured according to ISO 9276. The pellets may have a size ranging from 20 to 400 kg / m 3 Range Further, the pellets may have a particle density of 10 to 350 μm. (mean cell diameter).

[0012] A further aspect of the present invention is a method for producing a cushioning element for sports apparel. , in particular the use of expanded polymer pellets for producing shoe soles.

[0013] A further aspect of the present invention is a polymeric composition produced using the expanded polymer pellets described above. The present invention relates to a cushioning element for sports apparel, in particular a shoe sole or part thereof.

[0014] A further aspect of the invention relates to a shoe, in particular a sports shoe, having a sole as described above.

[0015] A further aspect of the invention is a polyamide-based thermoplastic resin that can be used in the temperature range from -40°C to +40°C. The expanded polymer pellets exhibit a change in storage modulus of less than 50% at .

[0016] A second aspect of the present invention is a. filling a mold with pellets of an expanded polymeric material; and b. consolidating the pellets by supplying thermal energy; Including, c. the expanded polymeric material of the pellets comprises a chain extender; The present invention relates to a method for the manufacture of a molded component.

[0017] In an exemplary embodiment, the chain extender was provided after polymerization of the polymeric material.

[0018] In another exemplary embodiment, the expanded polymeric material comprises a semi-crystalline polymer.

[0019] In step b., the thermal energy is pressurized steam, electromagnetic radiation, radio frequency radiation, microphone The radiation may be provided by at least one of microwave radiation, infrared radiation, ultraviolet radiation, and electromagnetic induction.

[0020] In one embodiment, during step b., the pellets are formed of a glass of expanded polymeric material. In an exemplary embodiment, the PET is heated to a temperature between the glass transition temperature and below the melting initiation temperature. The reed is heated to a temperature between 100°C and 5°C below the melting point of the expanded polymeric material. These are 60°C to 5°C below the melting point of the expanded polymer material, e.g. -Can be heated to a range of 40°C to 5°C below the melting point of the material.

[0021] The chain extenders include polymeric materials containing epoxy groups, pyromellitic dianhydride, and styrene. styrene maleic anhydride, or a combination of one or more of these In one embodiment, the chain extender may comprise at least one selected from the group consisting of a reaction Styrene-acrylate copolymers containing reactive epoxy groups, for example those of the formula:

[0022] [ka] (wherein R1 through R5 are H, CH3, a higher alkyl group, or a combination thereof; R6 is an alkyl group, and x, y, and z are each between 1 and 20. It is a compound.

[0023] In another embodiment, the chain extender is one or more of a triepoxide or a tetraepoxide. The chain extender is, for example, selected from triglycidyl isocyanurate and and / or tetraglycidyldiaminodiphenylmethane. The chain extender is selected from one or more of styrene, maleic anhydride, and In one embodiment, the chain extender is pyromellitic dianhydride.

[0024] In one embodiment, the polymer is a polyamide, a polyester, a polyetherketone, and polyolefins. The polyamide is selected from at least one of homopoly Among amides, copolyamides, polyether block amides, and polyphthalamides The polyester may be at least one of polybutylene terephthalate (PBT), Thermoplastic polyester ether elastomer (TPEE) and polyethylene terephthalate Polyetherketone can be at least one of polyether ketone (PET). Polyetherketone (PEK), Polyetheretherketone (PEEK), and Polyether The polyolefin may be at least one of poly(ethylene glycol ketone) and poly(ethylene glycol ketone). Propylene (PP), polyethylene (PE), olefin co-block polymer (OBC) ), polyolefin elastomer (POE), polyethylene-co-vinyl acetate (EVA), At least one of polybutene (PB) and polyisobutylene (PIB) obtain.

[0025] In another embodiment, the polymer is polyoxymethylene (POM), polyvinyl chloride, Polyvinyl alcohol (PVAL), polylactic acid (PLA), polytetrafluoroethylene (PVCD), Polytetrafluoroethylene (PTFE), Polyvinylidene fluoride (PVDF), Tetrafluoroethylene Ethylene (TFE), Ethylene-Tetrafluoroethylene (ETFE), Polyvinyl Fluoride Polyvinyl chloride (PVF), perfluoroalkoxy (PFA), and thermoplastic polyurethane (TP U).

[0026] In an exemplary embodiment, the polymer comprises polybutylene terephthalate (PBT). , the chain extender is a polymeric material containing an epoxy group, pyromellitic dianhydride, styrene anhydride at least one selected from maleic acid, In particular, it includes styrene-acrylate copolymers containing reactive epoxy groups. In form, the polymer may be polyamide (PA) or polyether block amide (P The chain extender is a polymer material containing an epoxy group, pyromellitic dianhydride. styrene maleic anhydride, or a combination of one or more thereof. At least one of them, in particular a styrene-acrylate copolymer containing reactive epoxy groups. In a further exemplary embodiment, the polymer is a thermoplastic polyester ether elastomer. The chain extender includes a polymer material containing an epoxy group, pyromellitic acid. Selected from dianhydrides, styrene maleic anhydride, or combinations of one or more of these At least one of the above is preferably a styrene-acrylate copolymer containing reactive epoxy groups. Includes.

[0027] A further aspect of the present invention is a. filling a mold with pellets of expanded polymeric material, the expansion of the pellets the polymeric material comprising an additive that increases the amorphous content of the polymeric material; and b. The pellets are heated to a temperature between the glass transition temperature and the melting onset temperature of the expanded polymeric material. consolidating the pellets by heating to a temperature; The present invention relates to a method for the manufacture of a molded component, comprising:

[0028] In one embodiment of the process of the second or further aspect, the pellets are a. melting a polymeric material, the melt comprising at least one polymer and at least one blowing agent and a chain extender, or the amorphous content of the polymeric material. and at least one of the additives that increase b. forcing the melt through at least one die to produce an expanded polymeric material Inflating; and c. The expanded polymeric material is pelletized, especially in an underwater pelletizer. P; It is produced by a method comprising:

[0029] In some embodiments, the pellets are produced by the method according to the first aspect of the invention. can be.

[0030] The chain extender provides amorphous regions in the expanded polymer material and interfaces at the pellet boundaries. In particular, in an amount that allows interdiffusion of polymer chains across 100% by weight of the base polymer 0.1 to 20% by weight, in particular 1% to 10% by weight, based on the material, e.g. It may be added in an amount of from about 5% to about 5% by weight.

[0031] The base polymer material may be a polyamide, such as a homopolyamide, a copolyamide, a polyamide, at least one of polyphthalamide, e.g., poly(ether block amide); It may also be triamide 12.

[0032] Chain extenders are polymeric materials containing epoxy groups, e.g., styrene containing reactive epoxy groups. The polymer may be a methacrylate-acrylate copolymer.

[0033] The pellets of expanded material have at least a partially ruptured foam structure therein. This can be done.

[0034] Further aspects of the invention include those described above with respect to the second or further aspects of the invention. It relates to the articles obtainable by the method.

[0035] In an exemplary embodiment, the article has an at least partially popped foam structure therein. Such articles are manufactured using pellets of expanded material that can be used for, for example, soundproofing. can be used for

[0036] Another aspect is a method for manufacturing a packaging material, a reusable packaging material, a pallet, an article for medical transport, a chemical Goods for transporting academic goods, goods for transporting fragile goods, goods for internal insulation, goods for external insulation products for pipe insulation, geofoam, temporary housing, road construction Rush prevention materials, articles for insulation of equipment, articles for insulation of industrial equipment, sun visors, Dashboard, car seat, center console, car door, child / baby seat Battery covers / insulation items, engine insulation items, bumpers, Shell structures, protective helmets, protective clothing articles, boat fenders, medical stretchers boards, surf / rescue boards, buoys, boat hulls, snowmobile seats, skis / skis Cores for Noboard / Waterski / Wakeboard, Jet Ski Seats, Artificial Turf , Flooring materials for venues or sports grounds, Protective flooring materials for sports halls / Wall materials, conditioning rollers, resistance weights for aerobics (resistance weights) stance weight, swimming aids, furniture items, bean bags, cow bedding mats, Drones, luggage items, airplane seats, airplane / glider wings, airplane covers Products for bottle insulation, airplane food trays, and airline food wagon insulation Products, underfloor materials, items for preventing overheating, items for advanced protective equipment, medical cast bandages, tarpaulins, etc. Bottle / rotor cores, run-flat tires, hand grips, beverage insulation, lamp covers , the article described above being provided as at least one of a mattress.

[0037] Another aspect is the manufacture of cushioning elements for sports apparel, in particular shoe soles, preferably Preferably, the method for producing an insole is produced according to the second or further aspect of the invention. Concerning the use of the items.

[0038] Another aspect is packaging applications, reusable packaging, pallets, medical transport, chemical transport, fragile and Transportation of contaminants, internal insulation, external insulation, pipe insulation, geofoam, temporary housing, road crash Prevention, equipment insulation, industrial equipment insulation, sun visors, dashboards, car seats, centers - Consoles, car doors, child / baby seats, battery covers / insulation, engine Insulation, bumpers, crash structures, protective helmets, protective clothing, boat fenders, medical Medical stretchers, surf / rescue boards, buoys, boat hulls, snowmobile hulls Core for skiing / snowboarding / water skiing / wakeboarding, jet skiing -sheets, artificial turf, venue or sports ground flooring, sports hall protective flooring / Wall, conditioning roller, resistance weights for aerobics, swimming Assistive devices, furniture, bean bags, cow mats, drones, travel bags, airplane seats, Airplane / glider wings, airplane cabin insulation, airplane food trays, airline flight food Dwagon insulation, underfloor, heat prevention, advanced protective equipment, medical cast bandages, turbine / rotor blades A, run-flat tires, hand grips, beverage insulation, lamp covers, mattresses of the second or further aspect of the invention.

[0039] Further aspects of the invention include those described above with respect to the second or further aspects of the invention. It also relates to an element obtainable by the method, in particular a shoe comprising a sole. By using the method described above with respect to the second or further aspect of the invention. The present invention relates to a shoe that includes a molded foam element.

[0040] Preferred embodiments of the invention are set forth in the following description, drawings and claims. do. [Brief description of the drawings]

[0041] [Figure 1] 1 shows an experimental set-up for carrying out steps a. to c. of the method according to the invention. [Diagram 2] FIG. 2 shows a schematic diagram of an underwater pelletizing apparatus for carrying out step d. of the method according to the invention. [Diagram 3] FIG. 2 shows a schematic diagram of the die face plate of the underwater pelletizer. [Figure 4]FIG. 1 shows storage modulus versus temperature for expanded polyamide pellets (ePA12) produced in Example 1, and comparative expanded polypropylene (ePP). [Figure 5-1] FIG. 5a shows the hysteresis loop for a test plate made from expanded polyether block amide pellets produced in Example 2, where the area under the compression branch of the hysteresis loop is shaded. [Figure 5-2] Figure 5b is the same as Figure 5a, with the portion of the hysteresis loop shaded, and Figure 5c shows the hysteresis loop for a test plate made from expanded polyether block amide pellets (ePEBA) produced in Example 2, compared to a test plate made from expanded polypropylene (ePP). [Figure 6] 1 shows a scanning electron microscope (SEM) image of expanded polyamide pellets produced in Example 1. [Figure 7] 1 shows a scanning electron microscope (SEM) image of expanded polyether block amide pellets produced in Example 2. [Figure 8-1] Figure 8a shows the mould when filled with pellets of expanded polymeric material, and Figure 8b shows the mould of Figure 8a when filled with pellets of expanded polymeric material. [Figure 8-2] FIG. 8c shows the version of FIG. 8b when thermal energy is applied to the pellet. [Figure 9] FIG. 1 shows heat flow versus temperature for expanded polyether block amide pellets with various amounts of chain extender (CE). [Figure 10] FIG. 1 shows a midsole made by fusing expanded polyether block amide pellets with a chain extender (CE). [Figure 11] FIG. 1 shows heat flow versus temperature for expanded polyether block amide pellets with various amounts of chain extender (CE). [Figure 12]FIG. 1 shows a midsole made by fusing expanded polyether block amide pellets with a chain extender (CE). [Figure 13] FIG. 1 shows heat flow versus temperature for expanded polybutylene terephthalate (PBT) pellets with various amounts of chain extender (CE). [Figure 14] FIG. 1 shows heat flow versus temperature for expanded thermoplastic polyester ether elastomer (TPEE) pellets with and without chain extender (CE). [Figure 15] FIG. 1 shows normalized melt energy versus chain extender (CE) content for expanded thermoplastic polyester ether elastomer (TPEE) pellets with and without chain extender (CE). [Figure 16] FIG. 1 shows a scanning electron microscope (SEM) image of expanded polyamide (PA12) pellets / beads. [Figure 17] FIG. 1 shows a scanning electron microscope (SEM) image of expanded polyamide (PA12) pellets / beads containing a chain extender (CE). DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0042] In the following detailed description, preferred examples and embodiments of the invention are described.

[0043] First aspect of the present invention The polymer used to prepare the expanded polymer pellets is at least one polyamide. The polymer may be polyamide-based. In particular, the polymer may be In this case, at least 10% by weight, in particular at least 30% by weight, based on 100% by weight of the polymer. %, preferably at least 50% by weight of polyamide. In this case, based on 100% by weight of the polymer, it is preferably from 10 to 99% by weight, more preferably from 25 to 30% by weight. 99% by weight, more preferably 50 to 99% by weight of polyamide. It is also possible for the composition to contain 100% by weight of polyamide or consist of 100% by weight of polyamide. be.

[0044] The polymer may be based on polyamide. In particular, the polymer may be in each case 10 0% by weight of the polymer, preferably at least 10% by weight, in particular at least 30% by weight. or at least 50% by weight of polyamide. Preferred ranges are 10 to 99% by weight, preferably 25 to 99% by weight, based on 100% by weight of the polymer. %, more preferably 50 to 99% by weight of polyamide. It is also possible for it to comprise or consist of 100% by weight of polyamide.

[0045] A suitable polymer is a polyamide or polyamide-containing polymer that is expandable. Particularly suitable are those having a tensile modulus of more than 10 MPa and / or It has a low temperature dependency. Suitable are, for example, polyamide-6 (PA6 ), Polyamide-6.6 (PA6.6), Polyamide-6.10 (PA6.10), Poly Amide-11 (PA11), Polyamide-12 (PA12), Polyamide-10.12, or polyamide-10.10. Combinations of these may also be used. The preferred ones are PA11 or PA12 or mixtures thereof. PA12 is used. Suitable polyamides, or polyamide-containing polymers, are commercially available. There are.

[0046] Particularly well suited are the polyether block amides (PEBA). Terephthalate block amides are block amides that have polyamide segments and polyether segments. For example, suitable polyether block amides are In this case, the amount is from 1 to 90% by weight, in particular from 1 to 100% by weight of the polyether block amide. % by weight, and from 10 to 99% by weight, in particular from 50 to 9 and a polyamide block content of 9% by weight. Blends or mixtures of two or more of the above. It is also possible, in particular, to use two different polyether block amides. %, or the polymer comprises 100% by weight of a polyether block amide. It is also possible for the polymer to be made of a polyether block amide. % polyamide and polyether block amide, or 100% polyamide It is also possible for the block amide to consist of a polyether block amide.

[0047] Particularly well suited are, in addition, the following properties: - Shore D hardness ranging from 20 to 70 Shore D, especially from 35 to 70 Shore D; - tensile modulus in the range from 10 to 1100 MPa, in particular from 80 to 1000 MPa; - 1000 to 1030 g / m 3 Density in the range of; - Melting point / melting range between 110 and 200°C, especially between 130 and 175°C and wherein the polyether block amide is a polyether block amide having at least one of the following:

[0048] In this specification, Shore D hardness is measured according to ISO 868. Tensile modulus Lath is measured according to ISO 527-1. Density is measured according to ISO 1183. In the present invention, the melting point or melting range, respectively, is determined according to ISO 11357. As used herein, the melting point or melting range of a polymer refers to the measurement of the temperature at which the polymer melts. This refers to the temperature, or temperature range, at which the crystalline regions of a crystalline polymer melt.

[0049] Suitable polyether block amides are commercially available. They can be prepared by known methods. For example, as described in WO 2006 / 045513. Thus, a polyamide block containing a reactive end and a polyether block containing a reactive end are It can be prepared by copolycondensation with

[0050] Of the polyamides and polyether block amides mentioned, mixtures or mixtures thereof are also preferred. A blend or mixtures of polymers may also be used. In addition to polyamides, other polymers, such as thermoplastic polyurethanes (TPUs), Polyphenylene Ether (PPE), Styrene-Acrylonitrile (SAN), and / or or rubber, especially TPU. The content of the polymer should be less than 50% by weight, especially less than 10% by weight, based on 100% by weight of the polymer. In one embodiment, the expanded pellets are produced by The polymer used for the coating is free of thermoplastic polyurethane (ie, 0%). In one embodiment, the polymer used to make the expanded pellets is a polyamide. Contains no polymers other than mide (i.e., 0%).

[0051] The polymer used to make the expanded pellets may be in any form, e.g. For example, the polymer may be used as a granule or powder, in particular as a granule. If the base or starting polymer contains adhering moisture or water, The polymer is preferably dried prior to melting, according to procedures known to those skilled in the art, and drying is carried out after the polymerization. Finished before the bubbles.

[0052] In the first step of the method according to the invention, the polymer is melted. Suitable methods for melting are known to those skilled in the art. Melting can be carried out, for example, in an extruder. Suitable extrusion equipment or extruders are not subject to any limitations. Extruders such as single or twin screw extruders can be used. The extruder can also extrude the polymer into a It serves to disperse the material evenly.

[0053] The main features of the extruder (e.g. type, length and speed of the extruder screw, temperature profile) The force (velocity, pressure) ensures that the applied material is uniformly dispersed and mixed into the molten polymer. The extruder can be selected by one skilled in the art so that the polymeric material is completely melted. The appropriate temperature depends on the polymer used and can be determined by one skilled in the art. For example, for polyamide 12, suitable temperatures range from 180° C. to 320°C, particularly in the range of 220 to 290°C.

[0054] It is also possible to use two extruders arranged in series. Good results have been obtained, e.g. When the first extruder is a twin screw extruder and the second extruder is a single screw extruder, The first extruder plasticizes the material and uniformly disperses added materials, such as foaming agents. Due to the inclusion of a blowing agent, the viscosity of the material is significantly reduced, making it easier to extrude the second part. The machine reduces the temperature of the material to improve the melt properties and increase the pressure required for foam expansion. It can also be used to heat a material and then cool it in a controlled manner. This can also be achieved by using a single screw extruder that is long enough to allow Additionally, a static mixer can be inserted between the first and second extruders. Suitable temperatures for the extruder 1 are from 170° C. to 320° C., particularly from 170 to 220° C., or The appropriate temperature for the second extruder depends on the polymer used. For example, for polyamide 12, the temperature range is from 150 to 190 °C, especially from 165 to Material temperatures in the range of 180°C are suitable, while for polyether block amides, 130 to Material temperatures of 180° C., especially in the range of 155 to 165° C., are suitable.

[0055] An exemplary arrangement 1 having a twin screw extruder 2 and a single screw extruder 9 is shown in FIG. According to FIG. 1, the polymer is introduced in a hopper 4 and the blowing agent 5 is introduced by an injection device 6. Further materials, e.g., chain extenders, are fed together with the polymer in hopper 4. and / or at or near the location of the injection device 6. The extruder 2 is driven through gear 3. In the extruder 2, the polymer is melted and , mixed with the injected foaming agent 5 and, optionally, additional materials added. According to the invention, an adapter 7 is provided between the extruder 2 and the extruder 9, and the extruder 9 is connected to the extruder 2 via a gear 8. The extruder 9 can be, for example, a cooling extruder. The polymer melt is further mixed with a blowing agent, cooled, and then passed through a die 11, preferably a circular The mixture is extruded through a die, resulting in a foamed or expanded extrudate 12. 1 is connected to an extruder 9 through an adapter 10 .

[0056] In one embodiment, at least one blowing agent is added to the molten polymer. Normally, with respect to volatile liquids, gases, and polymer melts under the conditions present in the extruder Any inert, decomposable compound that produces gas is suitable as a blowing agent. The blowing agent can be nitrogen, carbon dioxide, ethanol, isopropanol, or a mixture of these. Particularly well suited are supercritical carbon dioxide or supercritical carbon dioxide and ethanol. The blowing agent is premixed or mixed with the base polymer. Alternatively, the blowing agent may be added to the polymer melt without being added to the extruder. It may be added at an appropriate location and mixed in the extruder. Suitably the blowing agent is The amount of blowing agent added is 1 in each case. 00% by weight of the polymer melt, in the range of 1 to 20% by weight, in particular 1 to 10% by weight The specific amounts of blowing agent are 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, , 5, 7.5, 10 or 15% by weight. Particularly suitable are 100% by weight poly For example, 2 to 6% by weight of carbon dioxide and 2 to 4% by weight of ethanol are added to the melt. It is a carbon dioxide-ethanol mixture having a

[0057] In addition to the blowing agent, the usual further additives or materials that facilitate processing, such as nucleating agents, Chain extenders, flame retardants, plasticizers, strengthening agents, pigments, dyes, heat- or light-stabilizers, antistatic The additives, fillers, or mixtures thereof may be added to the polymer melt in the extruder. Suitable nucleating agents are either soluble or insoluble in the polymer melt to promote cell nucleation of the foam. Examples of insoluble nucleating agents include talc, or silica. It is also possible to add crosslinking agents to the polymer melt. Crosslinking agents are, for example, those listed in the International Publication Patent Application Publication No. 2006 / 045513 and European Patent Application Publication No. 1650255 In one embodiment, no crosslinking agent is used or the polymer -The pellets are not crosslinked.

[0058] In one embodiment, at least one chain extender is added to the polymer melt. It is also possible to feed at least one chain extender together with the polymer into the extrusion device. Suitable chain extenders are compounds that increase the melt strength of the polymer melt. Suitable chain extenders are oligomeric or polymeric compounds having reactive groups, such as epoxy groups. These react with the molten polymer to increase its molecular weight and branching, thus to improve the rheological properties, e.g., melt viscosity and melt strength, of the polymers used. Suitable chain extenders may be based on styrene-acrylate copolymers, Commercially available, for example, Joncryl® ADR-4368C from BASF The suitable amount of the chain extender is 0.05 to 10% by weight based on 100% by weight of the polymer. %, in particular 0.1 to 5% by weight, or 0.1 to 3% by weight. When using polyether block amide as the polymer for the production of stretched pellets, , is particularly beneficial.

[0059] In one embodiment, the polymer for making the expanded pellets is a polyether ether polymer. The chain extender further comprises a polyether block amide or a polyether block amide. It is added to the polymer melt as a dispersing material.

[0060] In addition, the polymer was extracted with granules from used tires (rubber) and raw rubber (caoutchouc It is also possible to melt the compound together with the powder. The thermal decomposition of the compound in the extruder produces decomposition gases. nitrogen and carbon dioxide, which can act as blowing agents; and the production of carbon, which can act as a reinforcing and nucleating agent. Leads to.

[0061] After extrusion, the melt is expanded through a die, which may be, for example, a circular die or It can be a slit die, especially a circular die. The diameter of the die depends on the size of the extruder, the desired particle size, and the Depending on the size and density of the particles, it may be in the range of, for example, 1 to 5 mm. The die pressure depends on the polymer material and density used. Depending on the specifications, it is in the range of 40 to 400 bar, especially in the range of 60 to 250 bar. Preferably, for polyamide, the pressure is in the range of 80 bar to 220 bar. For polyether block amides, the pressure is between 45 bar and 200 bar. The material temperature at the die depends on the polymer melt and can range from 140 to 180 °C, in particular in the range of 150 to 170 °C.

[0062] Within the die, and especially after exiting the die, the melt experiences a sudden pressure drop that causes the polymer Depending on the shape of the die, the expanded or foamed polymer is Preferably, a circular die is used to obtain the strands. The expanded polymer or foam is stabilized by cooling. The pelletizer, water bath, conveyor belt, or foam strand shape can be adjusted If so, this can be done with a calibration unit.

[0063] The expanded polymer is then pelletized. Suitable pelletizing equipment is known to those skilled in the art. The pelletizing process is carried out in a variety of ways, for example, underwater pelletizing equipment or underwater granulators. For example, underwater pelletization allows for both controlled cooling and pelletization of the expanded polymer. This can be done in a machine such as this. Such machines are commercially available. Their work involves The polymer strands are cut into separate particles in a cutting chamber that is completely filled with water. The size of the cut particles depends on the cutting speed and the extruder / die. The appropriate temperature of the water in the cutting chamber depends on the throughput and on the size of the die. It is in the range of from 20 to 100°C, in particular from 50 to 100°C, preferably from 70 to 90°C. Due to the temperature difference between the extrudate expanded through the die and the water in the cutting chamber, The polymer immediately solidifies in the form of particles, preferably spherical particles. The underwater pelletizer is preferably located immediately after the die. Another suitable underwater pelletizer is described in U.S. Pat. No. 5,629,028. is.

[0064] FIG. 2 shows the die front plate 101, cutting blade assembly 102, and water circulation housing. 1 shows an exemplary arrangement of an apparatus 100 for underwater pelletization having a feedstock 103. As shown, the expanded polymer 12 (see FIG. 1) passes through the extruder die 104 and exits the die face. The cup is surrounded by water circulating through the plate 101 and then in the housing 103. The extruder die 104 cuts the extruded material into particles 105 by the extruder blade assembly 102. The expanded polymer 12 is then fed to the extruder 100 via the underwater pelletizer 100. The particles 105 exit the water circulation housing 103 and are transported to the underwater pelletizer 100. The pelletizer 100 is a gearbox that is connected to the feedstock 101 and is then dried (not shown). Powered by 106.

[0065] FIG. 3 is a schematic diagram of the die front plate 101 of the underwater pelletizer. Port 101 includes holes 107. The number of holes depends on the size or dimensions of the extrusion device. In an exemplary embodiment, the diameter of the holes is between 2.3 mm and 2.6 mm, and the number of holes is 1. There can be between 4 and 4 holes, for example 2 holes when using a 2.3 mm diameter.

[0066] The shape and size of the expanded polymer pellets can vary depending on, for example, the throughput of the extruder, the shape of the die, and the like. The shape, temperature and pressure at the die, water temperature and water pressure in the underwater pelletizer, The cutting speed of the cutting blade of the cutter can be adjusted. Selection of appropriate conditions is within the ordinary skill of a person skilled in the art. It is within the scope of skill and knowledge.

[0067] The expanded polymer pellets may have a spherical, elliptical, or triangular shape. In most cases, the pellets have a substantially spherical shape. They may range, for example, in size from 2 to 10 mm, measured according to ISO 9276, and and 20 to 400 kg / m 3 , e.g. 50 to 300 kg / m 3 The particle density in the range A suitable average cell diameter is in the range of 10 to 350 μm.

[0068] The invention also relates to a polyamide-based thermoplastic resin that operates in the temperature range from -40°C to +40°C. The storage modulus of the expansion agent exhibits a change of less than 40%, preferably in the range of 30 to 40%. Preferably, they have a density of 70 to 100 kg / m 3 of It has a range of densities.

[0069] The present invention further provides a polyether block amide-based and test plate. When formed, the pores are removed by 10 to 90%, preferably 10 to 35%, (10 or more times) The relative energy loss during the entire hysteresis cycle (after the - pellets. Preferably, they have a density of 50 to 90 kg / m 3 Density range of In this specification, the relative energy loss during the entire hysteresis cycle is The area (integral) within the lysis loop is the total energy applied during compression, i.e., force vs. Divided by the area (integral) under the compression branch of the hysteresis loop in the compression strain (displacement) diagram This is shown in Figures 5b and 5a, respectively, and in Example 2 below. and are further described.

[0070] Expanded polymer pellets can be used in a wide range of applications. The components are very light in weight and exhibit good temperature performance and temperature dependence. They are lightweight and have good elasticity over a wide temperature range. and processed to produce components that exhibit good energy resilience. It can be worked on.

[0071] Thus, the expanded polymer pellets can be used to make cushioning materials, for example for sports apparel. For example, in shoes, in particular running shoes, It is very well suited for producing soles for running shoes. The expanded polymer pellets are then molded into pellets having a shape corresponding to the component to be manufactured. The expanded polymer pellets are then filled into a mold having a cavity, in which the expanded polymer pellets are then filled into a mold having a cavity. By applying heat to the mold, for example by supplying pressurized steam to the mold, is linked to.

[0072] The present invention also provides sports apparel and It also relates to shoes, especially sports shoes.

[0073] Other applications in which expanded polymer pellets are used include cushioning or damping properties and and areas where high stability within a wide temperature range is desirable, e.g. in the automotive sector or the aviation industry They also form components with good energy absorption properties. They can also be used to construct components for automobile crash prevention, for example. It is suitable for

[0074] Second Aspect of the Invention In a second aspect, the present invention provides a method for producing a molded product comprising the steps of: forming pellets or beads of expanded polymeric material into a mold; and packing the pellets or beads by supplying thermal energy. The present invention relates to a method for the manufacture of a molded component, comprising joining the molded component and the molded component together, the method comprising the steps of: The expanded polymeric material in pellets or beads contains a chain extender. and "beads" are used interchangeably herein.

[0075] For example, the chain extender may be provided after polymerization of the polymeric material. In a separate compounding step and / or by expanding the polymeric material. The chain extender may be added immediately prior to the preparation of pellets of the expanded polymeric material. The chain extenders may be incorporated into the base polymer material used in the compounding step. Alternatively, the base polymer may be added to the polymer first. - The raw material is fed to a processing device, e.g., an extruder, through a feeder, e.g., a hopper, and then chain-extended. Lengthening agents may be added.

[0076] To coalesce the pellets, thermal energy can be provided in a variety of different ways. The energy may be provided, for example, in the form of pressurized steam supplied to the mold tool. Alternatively or additionally, thermal energy may also be provided by an electromagnetic field. The method may be, for example, by irradiating the mold and / or pellets with electromagnetic radiation. Electromagnetic radiation may be, for example, in the following frequency ranges: radio frequency radiation (30 kHz to 300 MHz); Hz), microwave radiation (300MHz~300GHz), infrared radiation (300GHz~4 00 THz), ultraviolet radiation (789 THz to 3 PHz), or one or more of the other frequency ranges. can be selected from a number of sources. Thermal energy can also be provided by electromagnetic induction. For example, the pellets can be heated by irradiating them with electromagnetic radiation or by electromagnetic induction. In order to increase the amount of heat energy absorbed by the pellets, an energy absorbing material is All of the possibilities listed above may be combined with each other.

[0077] During step b., the pellets are heated to a temperature above the glass transition temperature and melt onset temperature of the expanded polymeric material. The heating can be performed to a temperature between 100 and 2000° C. This heating increases the mobility of the amorphous chains and This leads to bead-to-bead fusion of the expanded polymer pellets. Preferably, the process is carried out above the glass transition temperature of the expanded polymeric material. In this process, the pellets are heated to a temperature between 100°C and 5°C below the melting point of the expanded polymeric material. They are heated to a temperature 60°C to 5°C below the melting point of the expanded polymeric material, e.g. The temperature is increased from 50°C to 5°C below the melting point of the stretched polymer material, or from 40°C to 5°C below the melting point of the stretched polymer material. Can be heated.

[0078] As used herein, the term "melting onset temperature" refers to the temperature at which a polymeric material begins to melt. This is measured, for example by DSC (differential scanning calorimetry), in a diagram of heat flow versus temperature. The temperature at which the heat flow increases can be determined as the melting initiation temperature. When used herein, the term "melting point" refers to the melting peak obtained, for example, by DSC. Suitable conditions for DSC are, for example, a temperature range of 25°C to 250°C and heating at 10 K / min. The glass transition temperature of the expanded polymeric material can also be determined, for example, by DSC. It is possible.

[0079] The chain extenders include polymeric materials containing epoxy groups, pyromellitic dianhydride, and styrene. At least one compound selected from the group consisting of maleic anhydride, phenylalanine, maleic anhydride, and combinations of two or more thereof. Suitable chain extenders include styrene-acrylate copolymers containing reactive epoxy groups. Polymers, for example those of the formula:

[0080] [ka] (wherein R1 through R5 are H, CH3, a higher alkyl group, or a combination thereof; R6 is an alkyl group, and x, y, and z are each between 1 and 20. Such a chain extender is Joncryl® ADR-4368C. It is commercially available as (BASF).

[0081] The chain extender may also be a triepoxide, a tetraepoxide, or a combination thereof. Suitable chain extenders are, for example, triglycidyl isocyanurate and / or terephthalic acid. Another suitable chain extender is styrene anhydride. Maleic acid. A further suitable chain extender is pyromellitic dianhydride.

[0082] The expanded polymeric material is a semi-crystalline polymer or at least one semi-crystalline polymer. The polymer blend may include a polymer blend comprising

[0083] The polymers in the expanded polymeric material are polyamide, polyester, polyetherketone , polyolefins, or combinations thereof. The polyamide may be a homopolyamide, Copolyamide, polyether block amide, polyphthalamide, or combinations thereof A very suitable material is polyether block amide (PEBA). Typically, the polyamide is the same as defined above in relation to the first aspect of the invention. The polyester may be polybutylene terephthalate (PBT), thermoplastic polyester, Polyester ether elastomer (TPEE), polyethylene terephthalate (PET), or a combination thereof. The polyetherketone may be polyetherketone (PEK ), polyetheretherketone (PEEK), and polyetherketoneketone (PE The polyolefin may be polypropylene, polyethylene, polyethylene terephthalate, polyethylene glycol, polyethylene glycol terephthalate ... Polyethylene (PE), Olefin Co-Block Polymer (OBC), Polyolefin Elastomer (POE), polyethylene-co-vinyl acetate (EVA), polybutene (PB), and polyisobutylene (PIB), or a combination thereof.

[0084] Other suitable polymers include polyoxymethylene (POM), polyvinylidene chloride (PVC D), polyvinyl alcohol (PVAL), polylactic acid (PLA), polytetrafluoroethylene Polyethylene (PTFE), Polyvinylidene fluoride (PVDF), Tetrafluoroethylene (F EP), Ethylene-Tetrafluoroethylene (ETFE), Polyvinyl Fluoride (PVF) , perfluoroalkoxy (PFA), thermoplastic polyurethane (TPU), or This is a combination of:

[0085] As an example, the polymer may include polybutylene terephthalate (PBT) and the chain extender may include As a further example, the polymer may include PBT, and the chain may include a polymer material that includes epoxy groups. The extender includes pyromellitic dianhydride. As a further example, the polymer includes PBT. In one embodiment, the chain extender includes styrene maleic anhydride. As a further example, the polymer includes PBT. The chain extender is a styrene-acrylate copolymer containing reactive epoxy groups, or Examples include Joncryl® ADR-4368C.

[0086] As another example, the polymer may be a polyamide, such as polyamide 12, or a polyether. The chain extenders include polymeric materials containing epoxy groups, such as polyether ether block amides (PEBAs). As a further example, the polymer may be a polyamide, such as polyamide 12, or Contains ether block amide (PEBA) and chain extender contains pyromellitic dianhydride As a further example, the polymer may be a polyamide, such as polyamide 12, or a polyamide 13. block amide (PEBA), and the chain extender includes styrene maleic anhydride. As a further example, the polymer may be a polyamide, such as polyamide 12, or a polyamide 13. The chain extender is a styrene containing reactive epoxy groups, including terbenza block amide (PEBA). - acrylate copolymers, or for example Joncryl® ADR-43 Includes 68C.

[0087] In a further exemplary embodiment, the polymer is a thermoplastic polyester ether elastomer. The chain extenders include polymeric materials containing epoxy groups. As an example, the polymer includes TPEE and the chain extender includes pyromellitic dianhydride. As a further example, the polymer may include TPEE and the chain extender may be styrene maleic anhydride. As a further example, the polymer may include TPEE and the chain extender may include a reactive epoxy acid. Styrene-acrylate copolymers containing silyl groups, or, for example, Joncryl® Trademark) ADR-4368C.

[0088] In a further aspect, the present invention provides a method for producing a mold comprising filling a mold with pellets of an expanded polymeric material. and wherein the expanded polymeric material of the pellets has an amorphous content of the polymeric material. and incorporating an additive to increase the glass transition temperature of the expanded polymeric material. The pellets are consolidated by heating to a temperature between the melting point and the melting point. and; wherein the heating is as described above. Additives for increasing the amorphous content of polymeric materials This modifies the polymer so that better interlocking of the pellets in the mold is achieved. Such additives can be, but are not limited to, chain extenders.

[0089] The pellets used to manufacture the molded components may contain chain extenders or is any additive that increases the amorphous content of a polymeric material, or a combination of these. The composition may be prepared by using the method described above using a combination of the two. It is also possible to have more than one melt stage. , adding in two or more melt stages prior to expansion, e.g., melting the polymer and Chain extenders or additives are added, then cooled to melt the polymer, and blowing agents are added. It is also possible to melt the polymer and add a chain extender. Addition of the blowing agent is then followed by cooling and repeating the process.

[0090] The chain extender may be present in an amount of from 0.1 to 20% by weight based on 100% by weight of the base polymer material, particularly 0.1 to 15% by weight, preferably 0.1 to 10% by weight, for example 0.1 to 5% by weight %, or 1 to 5% by weight of the polymeric material. Additives that increase the content may also be used.

[0091] Particularly suitable base polymer materials are selected from polyamides, for example homopolyamides. , copolyamides, polyether block amides, and polyphthalamides. One example that is suitable is polyamide 12.

[0092] Chain extenders are polymeric materials containing epoxy groups, e.g., styrene containing reactive epoxy groups. The polymer may be a methacrylate-acrylate copolymer.

[0093] 8a, 8b and 8c show a moulded component according to a second embodiment of the invention. FIG. 8a shows a mold that can be used to carry out the method for manufacturing. 2 shows a mold as a whole, comprising two parts 201 and 202. The mold 200 is It has a cavity 205 which is filled with pellets 220 through a feed tube 210. FIG. 8c shows when the cavity 205 is completely filled with pellets 220. It shows the application of thermal energy 230 to the pellets 220 to bond the pellets together. After the pieces are joined, the mold 200 is opened by the parts 201 and 202 to form the molded The attached components can then be removed (not shown).

[0094] The molded components are inflated using steam-chest molding. This technology, as well as steam-chilling, can be used to produce fluororesin-based polymer pellets. Steam-chest molding machines are known in the art. Such machines are commercially available, for example, from Kurtz GmbH (Germany). First, the pellets are fed into a mold. After closing the mold, the pellets are placed under steam pressure. The conditions used for steam pressure and temperature depend on the pellet material used (po These conditions depend on the material (polymer, chain extender, additives, etc.). These conditions can be determined using routine experimentation. The temperature, on the one hand, causes the amorphous regions in the polymer to move further. On the other hand, the glass transition temperature of the polymer material is exceeded so that the foamed pellets can be easily Below the melting point of the polymer material so that the sheet does not begin to melt and eventually collapse. By way of example, molding can be performed at a temperature / pressure of 0.5-100° C. for a predetermined duration. This can be accomplished using a steam operating profile that increases or decreases the steam concentration. Suitable pressure, temperature and time / cycle conditions, e.g. balancing pressure and time If the pressure is too high, the pellets may collapse and melt. If the temperature is too low, the pellets may not receive enough energy and may not fuse properly. It is also possible to use a melt of a polymeric material to produce the fusion bond, e.g. In expanded polypropylene, which has two melting peaks, fusion occurs at the occurs between

[0095] The pellets of expanded material have at least a partially ruptured foam structure therein. It is possible.

[0096] The article may be a sheet of expanded material having an at least partially ruptured foam structure therein. When using a fluororesin, the molded components produced can be used for e.g. Suitable for.

[0097] The manufactured moulded components are used in packaging materials, reusable packaging materials, pallets , items for medical transportation, items for transporting chemicals, items for transporting fragile items, Products for internal insulation, products for external insulation, products for pipe insulation, geofoam, temporary Housing, road crash prevention materials, items for insulating equipment, items for insulating industrial equipment , sun visors, dashboards, car seats, center consoles, car doors, child seats car seats, battery covers / insulation items, engine insulation items, Bumpers, crash structures, protective helmets, protective clothing articles, boat fenders, medical For stretchers, surf / rescue boards, buoys, boat hulls, snowmobile sea Core for skiing / snowboarding / water skiing / wakeboarding, jet skiing Seats, artificial turf, venue or sports ground flooring, sports hall protective flooring materials / wall materials, conditioning rollers, resistance weights for aerobics, Swimming aids, furniture items, bean bags, cow mats, drones, travel bag items, Airplane seats, airplane / glider wings, articles for aircraft cabin insulation, airplane Food trays, items for insulating food carts on airline routes, underfloor materials, items for preventing overheating supplies, items for advanced protective equipment, medical casts, turbine / rotor cores, runflaps tires, hand grips, beverage insulation, lamp covers, mattresses As one may be used or may be suitable.

[0098] The manufactured moulded components are used as cushioning elements for sports apparel. It can be used as an article in the manufacture, in particular for the manufacture of shoe soles, preferably insoles. , or as may be appropriate.

[0099] Aspects of the invention relate to shoes, and in particular to shoes that include a cushioning element. It may be a sole, in particular an insole. Suitable insoles are, for example, expanded polyethersulfones, which contain chain extenders. Such midsoles can be made by fusing lubric amide pellets. 10 and 12, and further described in Examples 3 and 4 below.

[0100] Another aspect of the invention relates to an article comprising a foam. The foam can be produced using the method described above. The article can be made by fusing or joining expanded polymer pellets. , sports apparel, such as shoes, for example athletic shoes. The shoes may be provided with cushioning elements in the form of For example, the sole or insole may comprise foam.

[0101] The moulded components can also be used for soundproofing. The component is in particular a foam having an open-cell morphology. The fused foam may also have an at least partially ruptured structure. Suitable pellets or fused foams for producing sound articles include, for example, polyamides, e.g. For example, it may be made from polyamide 12. The polyamide may contain a chain extender. The stretched pellets are shown in Figures 16 and 17. Figure 16 shows the results for the pellets without chain extender (i.e. Scanning electron microscope (SEM) images of expanded polyamide (PA12) pellets at 0% FIG. 17 shows the results of the analysis of expanded polyamide (PA12) pellets containing 1.5% chain extender. 1 shows scanning electron microscope (SEM) images of the sintered material. The magnification scale in these figures is as indicated. These figures are based on the percentage of chain extender. Increasing the temperature causes the bubbles to burst. EXAMPLES

[0102] The present invention is illustrated by the following examples which show embodiments but do not limit the invention.

[0103] [Example 1] As the base polymer, a polyamide 12 material was used. Vest, available from Evonik Industries AG (Marl) The foaming agent was amid LX 9012. A combination of 4% (supercritical) carbon dioxide and 3% ethanol by weight was used. .

[0104] The base polymer and the blowing agent are fed into a twin-screw extruder 2 (see FIG. In extruder 2, The polymer introduced through the hopper 4 is melted and mixed with the injected blowing agent 5. The temperature profile in extruder 2 was in the range of 170 to 220°C. In extruder 9, the polymer melt was further mixed with a blowing agent and cooled. The material temperature at this stage was 170°C. The molten polymer was then heated to a pressure of 220 bar. The mixture was then expanded through a circular die 11 to obtain strand-like expanded extrudate 12. After that, the expanded extrudate 12 was fed to the underwater pelletizer shown in FIG. The temperature in the water circulation system of the retinizer was 70° C. The resulting pellets were After pelletization, the pellets were dried before density measurement. They had a density of 89 kg / m 3 The density of had.

[0105] The pellets were subjected to dynamic mechanical analysis (DMA) to evaluate their storage modulus at various temperatures. To clarify the mechanism, the structures were further examined by scanning electron microscopy (SEM).

[0106] DMA uses known testing equipment and performs storage modulus analysis from -40°C to +40°C. A temperature sweep was performed under the following test conditions: constant increments of 5°C; 5 minutes at each temperature. immersion time; 25% initial compressive strain; 5% sinusoidal oscillation around the initial strain; and 1 Hz The pellets tested had a substantially spherical shape and a diameter of about 5 mm. The results are shown in Figure 1, which shows the storage modulus (kPa) vs. temperature (°C) for EPA12. For comparison, a spherical shape of about 4-5 mm in diameter and similar stiffness (stiffness) was used. Foamed polypropylene (BASF Neopolen P9230) with The measurements for K (EPP) are further shown in FIG.

[0107] As is clear from the figure, when the temperature is changed from -40°C to +40°C, the storage elasticity Compared to expanded polypropylene particles (EPP), which shows a reduction in the elastomer content by approximately 288%, the polyamide pellets The storage modulus of the EPA12 sample shows a change of about 35%, or more precisely, a decrease of about 35%. .

[0108] A scanning electron microscope (SEM) image of the expanded polyamide pellets is shown in Figure 6. The magnification scale is 20 times the distance of 1 mm shown. The image shows that the pellet is closed. The foam has a uniform particle skin and uniform cell size, thus providing excellent foam structure at the particle level. This indicates that the device has a structure.

[0109] [Example 2] PEBA material was used as the base polymer. The PEBA material used was Ev Vestamid, available from Onik Industries AG (Marl) According to the manufacturer's information, the number after the letter E corresponds to the ISO 868 The Shore D hardness is expressed by the Shore D hardness of the material. Vestamid E62-S3 has a Shore D hardness of 62. As a foaming agent, 4% by weight is added to 100% by weight of the base polymer. A combination of 100% (supercritical) carbon dioxide and 2% by weight ethanol was used. A chain extender based on acrylate copolymer was used. The chain extender was BASF's J-acrylate copolymer. Oncryl® ADR-4368C, 100% by weight of the base polymer In contrast, it was used in an amount of 2% by weight.

[0110] The base polymer, blowing agent and chain extender are mixed in a twin screw extruder according to the set up shown in Figure 1. 2 (reference symbols are the same as in the discussion of FIG. 1 above). In the process, the polymer introduced through the hopper 4 is melted and mixed with the injected blowing agent 5, The chain extender was mixed with the polymer as a dry blend in a hopper. The temperature profile in extruder 2 ranged from 170 to 220 °C. In the cooling extruder 9, the polymer melt is mixed with a blowing agent and a chain extender. The material temperature in extruder 9 was 158° C. The molten The polymer is expanded through a circular die 11 at a pressure of 200 bar to produce strands. Expanded extrudate 12 was obtained. The expanded extrudate 12 was then subjected to underwater filtration as shown in FIG. The temperature in the water circulation system of the underwater pelletizer was 70°C. The resulting pellets were dried after underwater pelletizing and prior to density measurement. They are 70kg / m 3 and was examined by scanning electron microscopy (SEM). .

[0111] In addition, to evaluate the mechanical properties, the pellets were bonded together by steam. A test plate was made. The test plate had a strength of about 84 kg / m 3 It has a density of 1000 mm and its compression behavior is The sham was tested for movement.

[0112] Compression tests were performed using known testing equipment at 23°C under the following test conditions: mm thickness specimen; 50% compression; heel stamp (50mm diameter); 50mm / min velocity; and a preload of 5 N. The results obtained are shown in Figures 5a, 5b and 5c. For comparison, a foamed polypropylene (BASF's Neopole) with similar stiffness properties was used. Measurements were performed on similar test plates made from EPP (P9230K; As shown in Figure 5c.

[0113] The graph in Figure 5a shows the thermal expansion of the test plate made from an expanded polyether block amide. The hysteresis loop for the first cycle of the test plate is shown, where The total energy applied between the two points is shaded. The graph in Figure 5b is the same as that in Figure 5a. The same graph is shown, but the area within the hysteresis loop is shaded. From the shaded area in Fig. 5a, the relative Energy loss (%) is calculated by dividing the area of ​​the shaded part in Figure 5b by the area of ​​the shaded part in Figure 5a. This can be calculated by dividing the area of ​​the expanded pellet by the area of ​​the expanded part of the pellet. The relative energy loss during the first hysteresis cycle for the test plate is approximately Further test cycles were performed and in the tenth cycle, the relative energy The energy loss was approximately 31%.

[0114] The graph in Figure 5c shows the results of the analysis of the expanded polyether block amide pellets (ePEBA). The hysteresis loop of the test plate was measured using expanded polypropylene pellets (eP The figures are compared to test plates made from ePEBA (P). The values ​​are based on the results for the ePEBA test plates at 5 Good mechanical properties during compression up to 0% compression set (displacement), good recovery (low plasticity) The results are illustrated with low deformation and low hysteresis, thus reducing the pressure when compared to the ePP plate. This indicates that the shrinkage characteristics are improved.

[0115] Figure 7 shows a scanning electron microscope (SEM) image of an expanded polyether block amide pellet. The images are shown. The magnification scale is 20 times the distance of 1 mm shown. The pellets have a closed particle skin and uniform cell size, thus ensuring a uniform particle condition. It is shown that it has an excellent foam structure.

[0116] [Example 3] PEBA material was used as the base polymer. The PEBA material used was Ev Vestamid, available from Onik Industries AG (Marl) E62-S3. In addition, styrene-acrylate copolymer-based chain extenders, That is, Joncryl (registered trademark) ADR-4368C (BASF) was used in a ratio of 100% by weight. % of the base polymer, and were used in amounts of 1%, 2%, and 2.5% by weight. For comparison, the base polymer was also tested without a chain extender. The same blowing agent as described in Example 2, together with the indicated amount of chain extender, were used in Example 1. The melt was then melted in an extruder in the same manner as in Example 2. The melt was then melted in a circular die in the same manner as in Example 2. and fed to an underwater pelletizer to obtain expanded pellets. Ta.

[0117] The pellets (before molding) were subjected to a temperature test at 25°C to 250°C for their heat flow-temperature behavior. The results were obtained by DSC measurements in the temperature range with a heating rate of 10 K / min. The results are shown in Figure 9, where the data from the first heating of the DSC measurements are used. In FIG. 9, the indications on the curves indicate the amount of chain extender and, if any, the amount of chain extender relative to zero. The offset of the curves is shown. The curves are offset by 0. As can be seen, the peaks and widths of the curves are It is not affected by the chain extender. However, the height of the peak increases with increasing amount of chain extender. The polymer is affected in that it decreases as the crystallinity of the polymer increases. This means that it decreases with increasing amount of chain extender.

[0118] Pellets containing 2.5% by weight of chain extender are filled into a mold, and steam is supplied to the mold. The mold was a mold for molding the insole of a shoe. 4 shows an image of the insole obtained after molding.

[0119] [Example 4] PEBA material was used as the base polymer. The PEBA material used was Ev Vestamid, available from Onik Industries AG (Marl) E55. Styrene-acrylate copolymer-based chain extenders, i.e., Jo Ncryl® ADR-4368C (BASF) was 100% by weight of the base polymer. The mer was used in amounts of 3%, 4.5%, and 5% by weight. Additionally, the base polymer was also tested without a chain extender. The polymer was The same blowing agent as used in Example 2 was added together with the indicated amount of chain extender. The melt was then expanded through a circular die as in Example 2. The mixture was heated to 300° C. and fed into an underwater pelletizer to obtain expanded pellets.

[0120] The pellets (before molding) were subjected to a temperature test at 25°C to 250°C for their heat flow-temperature behavior. The results were obtained by DSC measurements in the temperature range with a heating rate of 10 K / min. The results are shown in Figure 11, where the data from the first heating of the DSC measurements are used. In FIG. 11, the indications on the curves are the amount of chain extender and, if any, zero. The offset of the curves with respect to the With offsets of 0.5, 1, and 1.2. As can be seen, the height of the peaks is The effect is that the strength decreases with increasing amounts of chain extender. , meaning that the crystallinity of the polymer decreases with increasing amounts of chain extender.

[0121] Pellets containing 5% by weight of chain extender were loaded into a mold, and the mold was heated by supplying steam to the mold. The mold was a mold for molding shoe insoles. Figure 12 shows the molded The image of the midsole obtained is shown in FIG.

[0122] [Example 5] Polybutylene terephthalate (PBT) material was used as the base polymer. The PBT material used was Ultradur B4520 available from BASF. Styrene-acrylate copolymer based chain extenders, i.e., Joncryl (BASF registered trademark) ADR-4368C (BASF) is used for 100% by weight of the base polymer. The base polymer was also used in amounts of 1% by weight and 1.5% by weight. It was also tested without a chain extender. A compact material was produced and the method The process involved melting the mixture, adding a chain extender, and extruding the resulting material. The material is cooled and the heat flow-temperature behavior of the material is compared over a 10- to 250-℃ temperature range. The results were measured using a DSC with a heating rate of K / min. The test results are shown in FIG. In the figure, the data from the first heating of the DSC measurement was used. The indications on the curves include the amount of chain extender and, if any, the offset of the curve relative to zero. The curves are shown for the 1st and 2nd offsets, respectively, for better comparison. As can be seen, the peak of the curve has a height that is affected by the chain extender. The peak height decreases with increasing amount of chain extender. , meaning that the crystallinity of the polymer decreases with increasing amounts of chain extender.

[0123] [Example 6] The base polymer used was TPEE material. The TPEE material used was DS The styrene-acrylate copolymer was Arnitel EM400 available from M. A polymer-based chain extender, i.e., Joncryl® ADR-4368C (B ASF) was used in an amount of 2% by weight based on 100% by weight of the base polymer. For this reason, the base polymer was also tested without a chain extender. A dense material was produced, The method involves melting the polymer, adding a chain extender, and extruding the resulting material. The dense material was then cooled and the heat flow-temperature behavior of the material was measured from 25°C to 250°C. The results were measured using a DSC with a heating rate of 10 K / min in the temperature range of The results are shown in Figures 14 and 15, where the first heating of the DSC measurements The data was used. In FIG. 14, the indications for the curves are the amount of chain extender, and In some cases, the offset of the curves relative to zero is shown. One curve is shown for better comparison. , with an offset of 0.2 as shown. As can be seen, the peak of the curve is The peak height is decreased by the presence of the chain extender. That means that the crystallinity of the polymer is decreased by the addition of a chain extender. Furthermore, the curve is smoother when chain extender is added.

[0124] FIG. 15 shows that the melting energy (normalized) was increased when the chain extender was added at 2 wt.%. , which shows a significant decrease of 29% in the degree of crystallinity due to the addition of chain extenders. The same trend is seen in Figure 15 (normalized melt energy versus chain extender content). As in the case of the expanded PEBA of Example 4 above (Figure 11), and when plotting the results for the expanded PBT of Example 5 above.

[0125] [Example 7] As the base polymer, polyamide 12 (PA12) material was used. Riamide 12 is Vestamid LX 9012 (Evonik Industrial As a blowing agent, 100 wt. % of the base was A combination of 4% (supercritical) carbon dioxide and 3% ethanol by weight for the polymer Styrene-acrylate copolymer-based chain extenders, namely Jonc 100% by weight of the base polymer is ryl® ADR-4368C (BASF) were used in amounts of 0 and 1.5 wt. %.

[0126] The polymer was prepared as in Example 1 with the same blowing agent and the indicated amount of chain extender. The mixture was melted in an extruder. The melt was then expanded through a circular die, as in Example 1. The mixture was then subjected to an underwater pelletizing process to obtain expanded pellets.

[0127] Scanning electron microscope (SEM) images of expanded polyamide pellets are shown in Figures 16 and 17. FIG. 16 shows pellets without chain extender (0%) and FIG. 17 shows pellets with 1.5% chain extender. The scale of the enlargement in these figures is 100 μm as indicated. The images show that the pellets are It has a partially ruptured foam structure, as indicated by the rupture, and therefore has excellent sound insulation properties. It is shown that the foam structure has a It should be noted that the present invention includes the following aspects. [1] a. Melting a polymer comprising a polyamide; b. adding at least one blowing agent; c. expanding the melt through at least one die to produce an expanded polymer causing; and d. pelletizing the expanded polymer; 1. A method for producing expanded polymer pellets comprising: [2] The polyamide may be based on polyamide, copolyamide and / or polyether. The method according to [1], comprising a tert-butyl ether block amide. [3] The polyether block amide has the following characteristics: - Shore D hardness ranging from 20 to 70 Shore D; - tensile modulus in the range of 10 to 1100 MPa; - 1 to 100% by weight of said polyether block amide in each case % to 90% by weight of polyether blocks and 10 to 99% by weight of polyamide blocks. Rock content; - 1000 to 1030 g / m 3 Density in the range of; and - Melting point / melting range of 110 to 200°C; The method according to claim 2, further comprising at least one of the following steps: [4] The blowing agent is nitrogen, carbon dioxide, isopropanol, ethanol, or a mixture thereof. In particular, the blowing agent is a mixture of carbon dioxide and ethanol. The method according to any one of the items [1] to [3]. [5] In step b., a nucleating agent, a chain extender, or both are further added, in particular a chain extender. The method according to any one of [1] to [4], [6] The method according to any one of [1] to [5], wherein the die is a circular die. [7] Any of [1] to [6], wherein the pressure at the die is in the range of 70 to 250 bar. 2. The method according to claim 1. [8] Any of [1] to [7], wherein the material temperature at the die is in the range of 150°C to 170°C. 2. The method according to claim 1 . [9] The expanded polymer is pelletized in an underwater pelletizer, 8].

[10] Expanded polymer obtainable by the method according to any one of [1] to [9] - Pellets.

[11]

[10] has a size ranging from 2 to 10 mm measured according to ISO 9276. The expanded polymer pellets are shown in Fig.

[12] 20 to 400 kg / m 3

[10] or

[11] having a particle density in the range Expanded polymer pellets.

[13] Any one of

[10] to

[12] having an average bubble diameter in the range of 10 to 350 μm 2. The expanded polymer pellets according to claim 1.

[14] For producing cushioning elements for sports apparel, in particular for producing shoe soles Use of the expanded polymer pellets according to any one of

[10] to

[13] above.

[15]

[10] to

[13] , using the expanded polymer pellets. Cushioning elements for sports apparel, particularly shoe soles.

[16]

[15] A shoe, particularly a sports shoe, having a sole as described in the above.

[17] Based on polyamide, its storage modulus is in the temperature range of -40°C to +40°C. The expanded polymer pellets show less than 50% change.

[18] a. filling a mold with pellets of an expanded polymeric material; and b. coalescing said pellets by supplying thermal energy; Including, c. the expanded polymeric material of the pellets comprises a chain extender; A method for the manufacture of a molded component.

[19] 18. The method of claim 17, wherein the chain extender is provided after polymerization of the polymeric material.

[20] The method according to claim 18, wherein the expanded polymer material comprises a semi-crystalline polymer. Method of posting. [twenty one] The thermal energy may be pressurized steam, electromagnetic radiation, radio frequency radiation, microwave radiation, infrared radiation, , ultraviolet radiation, or electromagnetic induction.

[18] ~

[20] 2. The method according to claim 1 . [twenty two] During step b., the pellets are heated to a temperature equal to or higher than the glass transition temperature of the expanded polymeric material. The method according to any one of

[18] to

[21] , wherein the composition is heated to a temperature between the melting initiation temperature and the melting initiation temperature. How to. [twenty three] During step b., the pellets are heated to a temperature 100° C. above the melting point of the expanded polymeric material. 5°C lower than the melting point of the expanded polymeric material, in particular 60°C to 5°C lower than the melting point of the expanded polymeric material. The method according to claim 0022, wherein the expanded polymeric material is heated to a temperature in the range of 40°C to 5°C below the melting point of the expanded polymeric material. [twenty four] The chain extender comprises a polymeric material containing an epoxy group, pyromellitic dianhydride, and sulfur. at least one selected from the group consisting of ethylene, maleic anhydride, and combinations of one or more thereof; The method according to any one of

[18] to

[23] , [twenty five] the chain extender is a styrene-acrylate copolymer containing reactive epoxy groups; In particular, the formula: [ka] (wherein R1 through R5 are H, CH3, a higher alkyl group, or a combination thereof; R6 is an alkyl group, and x, y, and z are each 1 to 20. The method according to claim 24, comprising:

[26] The chain extender is selected from one or more triepoxides or tetraepoxides, in particular Triglycidyl isocyanurate and / or Tetraglycidyl diaminodiphenyl methacrylate The method according to any one of

[18] to

[24] , wherein the compound is selected from the group consisting of

[27]

[18] The chain extender is selected from one or more of styrene maleic anhydride. A method according to any one of claims 1 to 7, wherein the method is a method according to any one of claims 24 to 7.

[28]

[18] to

[24] , wherein the chain extender is pyromellitic dianhydride. The method described.

[29] The polymer may be a polyamide, a polyester, a polyetherketone, or a polyolefin. The present invention relates to a method for producing a pharmaceutical composition comprising the steps of: How to.

[30] The polyamide may be a homopolyamide, a copolyamide, a polyether block amide, or and polyphthalamide.

[31] The polyester is polybutylene terephthalate (PBT), a thermoplastic polyester. Polyether elastomer (TPEE), and polyethylene terephthalate (PET) The method according to

[29] , wherein the method is at least one of the following:

[32] The polyetherketone may be polyetherketone (PEK), polyetheretherketone (PEK), At least one of the following: Polyetherketone (PEEK), and Polyetherketone (PEKK) The method according to

[29] ,

[33] The polyolefin may be polypropylene (PP), polyethylene (PE), or olefin. Co-block polymer (OBC), polyolefin elastomer (POE), polyethylene Polyvinyl acetate (EVA), polybutene (PB), and polyisobutylene (PIB)

[29] , wherein the method is at least one of the following:

[34] The polymer is selected from the group consisting of polyoxymethylene (POM), polyvinylidene chloride (PVCD), Polyvinyl alcohol (PVAL), polylactic acid (PLA), polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), tetrafluoroethylene (FEP) , Ethylene-tetrafluoroethylene (ETFE), Polyvinyl fluoride (PVF), Fluoroalkoxy (PFA), and Thermoplastic Polyurethane (TPU) The method according to any one of

[18] to

[24] , wherein the method is selected from one of the following:

[35] The polymer comprises polybutylene terephthalate (PBT) and the chain extender is Polymeric materials containing epoxy groups, pyromellitic dianhydride, styrene maleic anhydride, At least one selected from one or a combination of a plurality of these, particularly reactive epoxy Any one of

[18] to

[24] , including a styrene-acrylate copolymer containing a silyl group. The method according to claim 5.

[36] The polymer is polyamide (PA) or polyether block amide (PEBA). The chain extender comprises a polymeric material containing an epoxy group, pyromellitic dianhydride, sulfuric acid, and the like. at least one selected from the group consisting of ethylene, maleic anhydride, and combinations of one or more thereof; The method according to any one of

[0018] to

[24] , comprising the step of:

[37] the polymer comprises a thermoplastic polyester ether elastomer (TPEE); The chain extender is a polymeric material containing an epoxy group, pyromellitic dianhydride, styrene dianhydride, At least one selected from the group consisting of oleic acid, ... The method according to any one of

[18] to

[0024] , wherein the copolymer comprises a styrene-acrylate copolymer having a reactive epoxy group.

[38] a. filling a mold with pellets of expanded polymeric material, The expanded polymeric material may further comprise an additive that increases the amorphous content of the polymeric material. Contains; and b. The pellets are mixed with a mixture of the expanded polymeric material and a temperature that is less than the glass transition temperature and the melting onset temperature. consolidating the pellets by heating to a temperature between 23. A method for the manufacture of a molded component comprising:

[39] The pellets are a. melting a polymeric material, the melt comprising at least one polymer a polymer, at least one blowing agent, a chain extender, and an amorphous phase of the polymeric material. and at least one additive selected from the group consisting of additives for increasing the content of the component (a) and the component (b); b. passing the melt through at least one die to produce an expanded polymeric material. inflating through the c. pelletizing the expanded polymeric material, especially in an underwater pelletizer; Steps; The method according to any one of

[18] to

[38] , wherein the compound is produced by a method comprising the steps of:

[40] The method according to any one of

[0018] to

[38] , wherein the pellets are produced by the method according to any one of [1] to [9].

[41] The chain extender provides the expanded polymeric material with amorphous regions and provides a pellet boundary. In an amount that allows interdiffusion of polymer chains across the interface of the boundary, particularly in a 100 wt. % base Based on the polymeric material, from 0.1 to 20% by weight, in particular from 1 to 10% by weight, more particularly from 1 to 10% by weight, The method according to any one of

[18] to

[37] , wherein the compound is added in an amount of from 0.5 to 5% by weight.

[42] The base polymer material is a polyamide, in particular a homopolyamide, a copolyamide, a poly At least one of ether block amides, and polyphthalamides, preferably The method according to any one of

[30] and

[39] to

[41] , wherein the polyamide 12 is used. .

[43] The chain extender is a polymeric material containing epoxy groups, in particular a styrene containing reactive epoxy groups. The method according to

[42] , wherein the copolymer is a acrylate-acrylate copolymer.

[44] The pellets of the expanded material form an at least partially ruptured foam structure therein. The method according to

[42] or

[43] ,

[45] An article obtainable by the method according to any one of

[18] to

[44] .

[46] The article of

[45] manufactured by the method of

[44] .

[47] Packaging materials, reusable packaging materials, pallets, items for medical transport, items for transporting chemicals Articles for transporting fragile goods; Articles for internal insulation; Articles for external insulation , pipe insulation materials, geofoam, temporary housing, road crash prevention materials, equipment insulation Heating products, heat insulation products for industrial equipment, sun visors, dashboards, car seats Center console, car door, child / baby seat, battery cover / breaker Thermal articles, engine insulation articles, bumpers, crash structures, protective helmets t, protective clothing items, boat fenders, medical stretchers, surf / rescue boats Guards, buoys, boat hulls, snowmobile seats, skis / snowboards / water skis / Cores for wakeboards, jet ski seats, artificial turf, venue or sports field floors flooring materials, sports hall protection flooring materials / wall materials, conditioning rollers, Resistance weights for aerobics, swimming aids, furniture items, bean bags, Cow bedding, drones, luggage items, airplane seats, airplane / glider wings , items for insulating aircraft cabins, airplane food trays, airline food wagons Heat supplies, underfloor materials, heat prevention supplies, advanced protective equipment supplies, medical glove bandages, turbine / rotor cores, run-flat tires, hand grips, beverage insulation, The article of

[45] or

[0046] provided as at least one of a lamp cover and a mattress.

[48] In the manufacture of cushioning elements for sports apparel, in particular shoe soles, preferably midsoles 2. The use of an article according to

[45] for the manufacture of

[49] Packaging applications, reusable packaging, pallets, medical transport, chemical transport, fragile goods transport , interior insulation, exterior insulation, pipe insulation, geofoam, temporary housing, road crash prevention, equipment Thermal insulation, industrial equipment insulation, sun visors, dashboards, car seats, center consoles , Car Doors, Child / Baby Seats, Battery Covers / Insulation, Engine Insulation, Vans Per, crash structure, protective helmet, protective clothing, boat fender, medical stretcher Chars, surf / rescue boards, buoys, boat hulls, snowmobile seats, skis Core for snowboarding / water skiing / wakeboarding, jet ski seats, people Artificial turf, venue or sports field flooring, sports hall protective flooring / walls, training rollers, resistance weights for aerobics, swimming aids, furniture , bean bags, cow floor mats, drones, travel bags, airplane seats, airplane / grabs Aircraft Wings, Airplane Cabin Insulation, Airplane Food Tray, Airline Food Wagon Insulation , Underfloor, Heat prevention, Advanced protective equipment, Medical cast bandages, Turbine / rotor cores, Lanfla

[45] for tires, hand grips, beverage insulation, lamp covers, mattresses Use of items.

[50] The use of

[46] articles for soundproofing.

[51] The method according to any one of

[18] to

[44] can be used to obtain the above-mentioned A shoe with a support element, especially a sole.

[52]

[18] to

[44] A shoe with a foam element. [Explanation of symbols]

[0128] 1. Exemplary Arrangement 2 Twin screw extruder 3 Gear 4. Hopper 5. Foaming Agent 6 Injection device 7 Adapters 8 Gear 9. Single Screw Extruder 10 Adapters 11 Die 12 Foamed or expanded extrudates (polymers) 100 Equipment for underwater pelletizing 101 Die front plate 102 Cutter assembly 103 Water Circulation Housing 104 Extruder Die 105 particles 106 Gear 107 holes 200 Series Parts of the 201 model Parts of the 202 model 205 Cavity 210 Supply pipe 220 pellets 230 Thermal Energy

Claims

1. a. filling a mold with pellets of expanded polymeric material; b. consolidating the pellets by heating the pellets to a temperature between the glass transition temperature and below the onset of melting temperature of the expanded polymeric material; Including, the expanded polymeric material of the pellets comprises a chain extender; a base polymer material of the expanded polymer material is selected from at least one of polyether block amide, polyphthalamide, and thermoplastic polyester ether elastomer (TPEE); and The chain extender is a styrene-acrylate copolymer containing reactive epoxy groups and having the following formula: 【Chemistry 1】 wherein R1 through R5 are H, CH3, a higher alkyl group, or a combination thereof; R6 is an alkyl group; and x, y, and z are each 1 to 20; or The chain extender is triglycidyl isocyanurate and / or tetraglycidyldiaminodiphenylmethane, or the chain extender is styrene maleic anhydride; or The chain extender is pyromellitic dianhydride. A method for the manufacture of a molded component.

2. the chain extender is provided after polymerization of the base polymer material; or the expanded polymeric material comprises a semi-crystalline polymer; or 10. The method of claim 1, wherein the thermal energy for the heating is provided by at least one of pressurized steam, electromagnetic radiation, radio frequency radiation, microwave radiation, infrared radiation, ultraviolet radiation, and electromagnetic induction.

3. During step b., the pellets are heated to a temperature in the range of (i) 100°C to 5°C, (ii) 60°C to 5°C, or (iii) 40°C to 5°C below the melting point of the expanded polymeric material; 3. The method of claim 1 or 2, wherein the temperature at which the expanded polymeric material begins to melt, the melting point, and the glass transition temperature are measured by Differential Scanning Calorimetry (DSC).

4. The method of claim 1 , wherein the base polymer material is a polyether block amide.

5. the base polymer material comprises a polyether block amide and the chain extender comprises a styrene-acrylate copolymer containing reactive epoxy groups; or The method of claim 1 , wherein the base polymeric material comprises a thermoplastic polyester ether elastomer (TPEE) and the chain extender comprises a styrene-acrylate copolymer containing reactive epoxy groups.

6. The pellets are a. melting a polymeric material, the melt of the polymeric material comprising: (i) a base polymeric material selected from at least one of polyether block amide, polyphthalamide, and thermoplastic polyester ether elastomer (TPEE); (ii) at least one blowing agent; and (iii) the chain extender; b. expanding the melt through at least one die to produce the expanded polymeric material; c. pelletizing the expanded polymeric material in an underwater pelletizer; The method according to any one of claims 1 to 5, wherein the composition is produced by a process comprising:

7. 6. The method of any one of claims 1 to 5, wherein the chain extender is added in an amount of (i) 0.1 to 20 wt%, (ii) 1 to 10 wt%, or (iii) 1 wt% to 5 wt%, based on 100 wt% of the base polymer material.

8. the base polymer material is a polyether block amide; The method of any one of claims 4, 6, and 7, wherein the chain extender is a styrene-acrylate copolymer containing reactive epoxy groups.

9. The method of claim 8, wherein the pellets of the expanded polymeric material have at least a partially ruptured foam structure therein.

10. An article obtainable by the method according to any one of claims 1 to 9.

11. 11. An article according to claim 10 produced by the method according to claim 9; or Packaging materials, reusable packaging materials, pallets, articles for medical transport, articles for chemical transport, articles for transport of fragile goods, articles for internal insulation, articles for external insulation, articles for pipe insulation, geofoam, temporary housing, road crash protection, articles for equipment insulation, articles for industrial equipment insulation, sun visors, dashboards, car seats, centre consoles, car doors, child / baby seats, battery covers / articles for insulation, articles for engine insulation, bumpers, crash structures, protective helmets, articles of protective clothing, boat fenders, medical stretchers, surf / rescue boards, buoys, boat hulls, snowmobile seats, skis / snowboards / water skis / way 11. The article of claim 10 provided as at least one of: a core for a board, a jet ski sheet, artificial turf, venue or athletic field flooring, sports hall protective flooring / walling, conditioning rollers, resistance weights for aerobics, swimming aids, an article of furniture, a bean bag, a cow floor mat, a drone, an article of luggage, an airplane seat, an airplane / glider wing, an article for airplane cabin insulation, an airplane food tray, an article for airline food wagon insulation, an under-flooring, an article for overheating protection, an article for advanced protective equipment, a medical cast bandage, a turbine / rotor core, a run-flat tire, a hand grip, a beverage insulation, a lamp cover, and a mattress.

12. Use of an article according to claim 10 in the manufacture of a cushioning element for a shoe sole, or Packaging applications, reusable packaging, pallets, medical transport, chemical transport, fragile transport, interior insulation, exterior insulation, pipe insulation, geofoam, temporary housing, road crash protection, equipment insulation, industrial equipment insulation, sun visors, dashboards, car seats, center consoles, car doors, child / baby seats, battery covers / insulation, engine insulation, bumpers, crash structures, protective helmets, protective clothing, boat fenders, medical stretchers, surf / rescue boards, buoys, boat hulls, snowmobile seats, cores for skiing / snowboarding / water skiing / wakeboarding, geo 11. Use of an article according to claim 10 for wet ski sheets, artificial turf, venue or sports field flooring, sports hall protective flooring / walls, conditioning rollers, resistance weights for aerobics, swimming aids, furniture, bean bags, cow floor mats, drones, travel luggage, airplane seats, airplane / glider wings, airplane cabin insulation, airplane food trays, airline food wagon insulation, underfloors, heat protection, advanced protective equipment, medical cast dressings, turbine / rotor cores, run-flat tyres, hand grips, beverage insulation, lamp covers or mattresses; or Use of the article according to claim 10 for soundproofing.

13. A shoe comprising a sole obtainable by using the method according to any one of claims 1 to 9, or A shoe comprising a foam element molded by using the method according to any one of claims 1 to 9.

Images